Camille

Aquino
Enrico
Calma Jr.

L. 2011-01057-MN-0
2011-01677-MN-0
A.

Topic:
Recent Advances
Techniques

in

Voltammetric

BS Chemistry Prof Dalton R. Fortin Ms. C

4-1

Questions:
1. Is voltammetric technique considered qualitative or quantitative test?
Answer:
It can be considered as both quantitative and qualitative.
(Quantitative analysis of trace of metals (or, anyway, of those reducible or oxidizable
chemicals) at g/L levels or less.)
(Quali quantitative aspects of the voltammetric analysis can be used to trace of heavy
metals and of organic substances in solution.
2. Explain how the implantable glucose biosensor works.
Answer:
A sensor is implanted in the body (e.g. in wrist). A thermos responsive hydrogel is
required because it is a gel that when heat is applied, it collapses and when it cools down, it
re-swells. A watch like device connected to the implant will serve as the meter for the
glucose level signal.
3. What do you call the enzyme that is responsible for the redox reaction of bloods glucose in
glucose biosensor?
Answer: glucose oxidase
4. The rate of redox reaction between the glucose biosensor with enzyme called glucose
oxidase and blood is very crucial stage on determining persons blood sugar level. What do
you think is the reason behind this stage?
Answer:
The rate of reaction between the glucose oxidase in the sensor and the glucose component
of the blood dictates the level of glucose level of a person. The higher the redox reaction, the
higher the glucose level will be.

5. Explain why there is a need for a biosensor to have a hydrogel wrap compartment.
Answer:
Heating element will heat the skin and the membrane will collapse and it will kick off
cells and proteins (cleaning process). And so when it cools down and re-swells, then the

newly cleaned membrane allows the glucose to diffuse to it and will allow to resume
measuring glucose level.

I. Topic Outline
1. Definition of voltammetry and the principle behind this technique
2. Different types of voltammetric techniques and their uses
3. Recent Advances of voltammetric techniques
3.1 Determination of anions, different drug components and heavy metals
3.2 Voltammetry and its application in Implantable Biosensor
4. Challenges and Limitations of these advances
5. References

What is Voltammetry?
A method for determining the chemical makeup of a sample substance by
measuring electrical activity, or the accumulation of chemicals, on
electrodes placed in the substance. [1]
Voltammetric techniques are used as the basis of the comprehension of the
laws concerning several electrochemical phenomena and has a great
importance in several technological fields like:
a. Production of new type of batteries that can store rapidly great quantities of
energy.
b. Research of Corrosion proof materials.
If the electrode is formed by a drop of mercury rhythmically dropping from a
capillary, the analytical technique is called polarography.
What is the general principle behind the operation of voltammetry?
A time-dependent potential is applied to an electrochemical cell, and the
current flowing through the cell is measured as a function of that potential.
A plot of current as a function of applied potential is called a voltammogram
and is the electrochemical equivalent of a spectrum in spectroscopy,
providing quantitative and qualitative information about the species involved
in the oxidation or reduction reaction.

Figure 1 Example of Voltammogram and calibration

lines inserted obtained in the analysis of cadmium and
lead on one of the sampled trees in Pombal Square
Source: J. Braz. Chem. Soc. Vol.16 no.6a Sao Paulo
Nov./Dec.2005
http://dx.doi.org/10.1590/S010350532005000700028

Review of Different Voltammetric Techniques

Table 2 Different Voltammetric Techniques
Voltammetric Technique

Definition

1. Rapid
ScanThis - At the working electrode is
Voltammetric technique is
applied a rapid potential
the simplest technique.
scanning
that
varies
linearly (20 100 mV/s).
The scanning starts before
the discharging potential
and stops afterwards,
2. Cyclic Voltammetry- a - It is a particular LSV that
technique devote to the
perform
a
triangular
theoretical study of the
shaped scanning at the
behaviour
of
redox
working electrode. In this
couples.
way a redox couple in
solution is exposed before
to
an
oxidation
and
afterwards to a reduction
(or vice and versa).
3. Differential
Voltammetry
voltammetric
which
make

Uses
-For determination of
dopamine concentration in
vivo

It is often used to study a

variety of redox processes,
to determine the stability of
reaction products, the
presence of intermediates in
redox reactions,
reaction and electron
transfer kinetics, and the
reversibility of a reaction.

Pulse- A sequence of potential - Determination

of
A steps w/ each steps have a
antioxidant concentration
technique duration of 50 ms is
such as quercetin with a
use
of applied
to
working
detection limit of 6.77 ppb

potential pulse.

electrode.
at 15 s accumulation
- Charging constants decays
time.
rapidly and exponentially - Used in testing antifungal
hence observed current
concentrations.
late in the pulse life - Trace metal concentration
excludes charging current. - Useful
for
analysis
of
mixtures
- Provides information about
the chemical form of the
analyte.
4. Square
Wave - It consists of regular square
Voltammetry
wave, superimposed on
-Further improvement of
the base of staircase - One of the methods used in
the determination of drug
staircase
potential, and is applied to
component
such
as
voltammetry which is itself
the working electrode.
rifampicin norfloxacin.
a
derivative
of
linear - The current is doubled
Sample
may be expressed
sweep voltammetry.
during each square wave
in
submicromolecular
cycle, once at the end of
level.
the forward pulse and the
other at the end of the
reverse pulse.
- The difference between the
two
measurements
is
plotted versus the base
potential.
5. Hydrodynamic
- Electrogenerated
species - Chromatographic detection
Voltammetry
are rapidly swept away by - Determination of oxygen
- Performed by a rapid
the flow.
and glucose
stirring on the system.
- Reactants are carried to the - Detection of end point in
electrodes by migration in
volumetric titration
the field, convection and
diffusion. Migration rate is
independent on applied
potential.
6. Stripping Voltammetry
Stripping consists of two - Metal traces determination
- It is the method commonly (2) steps: Deposition and
in materials such as drugs
used
for
the
metal Stripping step.
- Innovative way of producing
determination of materials
antiretroviral
medicines
1.
Deposition
step
such as drugs, foods and
for HIV
-Involves
raw.
preconcentration.
- There are different versions
Requires
electrolytic
of
stripping
analysis
deposition
of
small
portion
depending on the nature
of metal ions in solution
of the deposition and the
into
a
electrode,
stripping steps.
commonly
used
in
mercury.
2. Stripping Step
- The measurement step.
- Involves
the
actual
dissolution (stripping) of

the deposits.

In summary, the main application of Voltammetry are the following:

1. Determination of concentration of certain species in a matrix
2. Determining the standard state potential
3. Multicomponent analysis

Recent Advances of Voltammetric Techniques:

1. Determination of anions, different drug components and heavy
metals (Anodic Stripping Voltammetry)
a. How it is done?
Voltammetric determination of different metal and compound in a
matrix is typically done using a three (3) electrode system consisting
Hanging mercury drop electrode (HMDE) as working electrode,
platinum as auxiliary electrode and Ag/AgCl/ KCl as reference
electrode. Ultra-pure water and acetated buffer (pH 4.6) was taken in
polographic vessel and the measurement was started under different
parameters.
Parameters include
Working electrode
Number of replications
Drop size
Stirrer speed
Purge time
Deposition potential
Deposition time
Voltage step
Voltage step time
Sweep rate
Peak potential

Challenges

Like other voltammetric techniques, anodic stripping voltammetry is

not free of interferences. In ASV, overlapping stripping peaks and
intermetallic compound formation.
The formation of intermetallic compound in or on the working electrode
may affect the size and position of the peak current for a particular metal.
Thus, finding an effective way to overcome this problem is another challenge
facing this method.
Limitations
As this voltammetric technique is used in component determination,
different parameters are considered throughout. Calibration method is done
using standard addition method and extra care in needed upon performing
the calibration.

Table 2 Representative Samples of Analytes Determined by Stripping

Voltammetry Source: Application of Modern Electroanalytical Techniques, Alpana
Gupta et. al. IJPSR (2013), Vol. 4, Issue 7

Anodic Stripping
Voltammetry
Bi3+
Cd2+
Cu
Ga3+
In3+
Pb2+
Tl+
Sn2+
Zn2+

Cathodic
Stripping
Voltammetry
Br _
Cl_
I_
Mercaptans
S2SCN-

Adsorptive
Stripping
Voltammetry
Bilirubin
Codeine
cocaine
digitoxin
dopamine
heme
monensin
testosterone

2. Voltammetry as Biosensors (cyclic voltammetry)

There is no doubt why voltammetry can now be used as biosensors like for
example in glucose determination. One of the reasons why is its low cost.
Accurate results can be obtained in just a short period of time requiring only a
small amount of sample.
2.1 A Glucose
Nanoparticles [4]

Biosensor

Based

on

Nanographene

and

ZnO

- A new glucose
immobilization of glucose

electrochemical

biosensor

was

made

based

on

oxidase (GOx) on zinc oxide nanoparticles (ZnO NPs) doped in nanographene

(NGs) sheets.
a. How it is done?
Glassy carbon electrode (3 mm-diameter) was polished first with 1.0,
and 0.05-m alumina Slurry then rinsed with distilled water and were
sonicated in absolute ethanol. A graphene ZnO composites is then added
to the glassy carbon allowed to dry in ambient air for 12 h to obtain
graphene-ZnO NPs modified electrode. Finally Nafion (5 wt. %) was
casted and used as a net to hold the GOx/ZnO NPs-NGs on the electrode
surface stably. The solvent was allowed to evaporate before use. The
glucose solutions were introduced into the sample loop by means of a
plastic syringe. [4]
Note. To prevent loss of the enzyme molecules, nafion films have been used
in the construction of biosensors. Nafion, due to its easy fabrication, good
electrical conductivity, high chemical stability and good biocompatibility, has
been widely used as a protective coating material and as a support for the
enzyme immobilization. [4]

Figure 2 Schematic diagram of the flow injection analysis

2.2 An Implantable Biosensor

[4]

It is biosensor that is placed inside the body of a person so that they

could monitor their glucose levels, blood sugar levels at all-time points.
A. How it is done?
A sensor is implanted in the body (e.g. in wrist). A cell cleaning
membrane like a thermos responsive hydrogel is coated to the sensor to
clean body cells that attached to the sensor first. A thermos responsive
hydrogel is required because it is a gel that when heat is applied, it
collapses and when it cools down, it re-swells. The idea is hydrogel will
wrap around the glucose sensor and it would be implanted just below the
skin and a watch like device is connected over the implant. This watch
like device will serve as the meter for the glucose level signal. A heating
element is also attached to the watch. Periodically, the heating element
will heat the skin and the membrane will collapse and it will kick off cells
and proteins (cleaning process). And so when it cools down and re-swells,
then the newly cleaned membrane allows the glucose to diffuse to it and
will allow to resume measuring glucose level.

b. Major Advancement of Glucose Biosensors

1. Non-invasive biosensors
2. Implantable glucose sensors

Note. As the research progresses, there are now different biosensor available to
humans. One of which is the cholesterol biosensors which usually based on the
cholesterol oxidation. Immunosensors which deals with the pathogenic bacteria
which causes disease (Biomarkers) and more recently, for the DNA hybridization
and damage.

Figure 3 Principle of electrochemical biosensor

[3]

Characteristic of Good Biosensor

1. Manufactured in large numbers and at low cost.
2. Rapid results within the timescale of the process/diagnostic test.
3. Self-calibrating.

Advantage
Having an implanted glucose biosensor can monitor glucose level would
really revolutionize how diabetics especially monitor their blood sugar levels

Limitations of Biosensors
1.

Biomaterials are fragile.

2.

Many materials needed.

3.

Integration
Includes Sensor system, Integration of several steps, multiple analytes.

4.

Miniaturization

Includes making integrated system smaller, mass production, and cheaper

components.

Challenges of Voltammetric Biosensors

1. Inputs are required from Biology, Chemistry, Material Science and Physics
2. More must still be done to realize the potential of biosensors.

References
[1] Detection of metals by differential pulse anodic stripping voltammetry
(DPASV) in pollen collected from a fragment of the Atlantic forest in Piracicaba/SP
T.A. daSilveira1et. al. Ecotoxicol. Environ. Contam., v. 8, n. 2, 2013, 31-36
[2] Different Kinetics Govern Dopaminergic Transmission in the Amygdala,
Prefrontal Cortex, and Striatum: An in vivo Voltammetric Study P. A. Garris and R.

M. Wightman Department of Chemistry and Curriculum in Neurobiology,

University of North Carolina at Chapel Hill, Chapel Hill, North Carolina, The Journal
of Neuroscience, 27599-3290
[3] Electrochemical Biosensors Modern and future approaches to medical
diagnostics James F. Rusling Dept. of Chemistry, Univ CT, Storrs, Dept. of Cell
Biology, Univ. of CT Health Center
[4] A Glucose Biosensor Based on Nanographene and ZnO Nanoparticles Using
FFT Continuous Cyclic Voltammetry Parviz Norouzi, Endocrinology and Metabolism
Research Center, Tehran University of Medical Sciences, Tehran, Iran Int. J.
Electrochem. Sci., 6 (2011) 5189 - 5199